JP2020158597A - Composite containing 3d structure in gel - Google Patents

Abstract

To provide a composite that can improve the shape retention of gel while imparting various shapes, and furthermore has an excellent vibration damping property.SOLUTION: A composite contains a 3D structure in gel. A composite, preferably in which, in the composite, the apparent volume fraction of the three-dimensional structure with respect to the complex is 70% or more; more preferably in which the 5% compressive hardness of the 3D structure is 0.5 N/φ100 mm or more and 10 N/φ100 mm or less; furthermore preferably in which the rate of change in mass of the gel after drying is 20% or more; and most preferably in which the vibration damping property is 80% or more.SELECTED DRAWING: None

Description

The present invention relates to a complex containing a three-dimensional structure in a gel, which is excellent in shape retention and can correspond to various shapes.

In general, a gel-like polymer substance containing water has a weak mechanical strength, and particularly when the polymer density in the gel is low, its shape retention becomes extremely poor, and it cannot withstand use in various applications. Therefore, conventionally, as a method of reinforcing such a gel-like polymer substance, a method of adhering the gel-like polymer substance on a solid having an appropriate strength or embedding a filler or short fibers in the gel is used. It has been known.

As a method for improving the shape retention of the gel, there are a method of adhering the gel on a solid and a method of embedding a filler in the gel. The method of adhering gel on a solid makes it difficult to give a complicated shape, and it is limited to applications that can be used as a plate material. Further, in the method of embedding the filler in the gel, since the fillers do not have a continuous structure, the stress received cannot be dispersed, and the effect of improving the shape retention is not sufficient.

Japanese Unexamined Patent Publication No. 10-52888 Japanese Unexamined Patent Publication No. 11-221104

An object of the present invention is to obtain a composite which can improve the shape-retaining property of a gel while imparting various shapes and further has an excellent vibration damping property.

As a result of diligent studies by the present inventor, it has been found that by encapsulating a three-dimensional structure in a gel, shape retention can be greatly improved, and a complex having excellent vibration damping properties can be obtained. It was.

That is, the present invention has the following configuration.
(Item 1)
A complex containing a three-dimensional structure in the gel.
(Item 2)
Item 2. The complex according to Item 1, wherein the apparent volume fraction of the three-dimensional structure with respect to the complex is 70% or more in the complex.
(Item 3)
Item 2. The composite according to Item 1 or 2, wherein the 5% compressive hardness of the three-dimensional structure is 0.5 N / φ100 mm or more and 10 N / φ100 mm or less.
(Item 4)
Item 2. The complex according to any one of Items 1 to 3, wherein the rate of change in mass of the gel after drying is 20% or more.
(Item 5)
Item 4. The complex according to any one of Items 1 to 4, which has a vibration damping property of 80% or more.

The composite of the present invention can significantly improve the shape retention without increasing the hardness of the gel itself, and can further obtain a composite having excellent vibration damping properties.

In the present invention, the complex containing the three-dimensional structure in the gel is not only a state in which the three-dimensional structure is completely contained in the gel, but also a part of the three-dimensional structure protrudes from the surface. It also includes the state of being.

In the composite of the present invention, the apparent volume ratio of the three-dimensional structure contained in the composite is preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, based on the volume of the composite. If the apparent volume fraction is less than 70%, the gel-only portion increases, the vibration is transmitted only to the gel portion, cannot be dispersed by the three-dimensional structure, and shape retention and vibration damping cannot be obtained. ..

Materials for forming the three-dimensional structure used in the present invention include thermosetting resins such as phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, polyurethane and polyimide, and polyolefin and polyester. , Polyamide, polyvinyl chloride, polystyrene, thermoplastic resins such as copolymers and elastomers copolymerized based on them, metals such as gold, silver, copper, iron and lead can be used.

The physical properties of the three-dimensional structure used in the present invention are not particularly limited, but the 5% compression hardness is preferably 0.5N / φ100mm or more and 10N / φ100mm or less, and 1N / φ100mm or more and 8N / φ100mm or less. Is more preferable. If the 5% compression hardness is less than 0.5 N / φ100 mm, the hardness is too low, so that the force cannot be dispersed and it is difficult to improve the shape retention. Further, if the 5% compression hardness exceeds 10 N / φ100 mm, the hardness is too high, so that the hardness difference from the gel becomes large, the gel becomes fragile, and the durability as a composite may be impaired.

In the present invention, the gel may be in a gel state regardless of whether it is oily or water-based, or it may be gelled with a gelling agent even if it is not in a gel state. Is 37 ° C. or higher and 41 ° C. or lower, preferably 38 ° C. or higher and 40 ° C. or lower), carrageenan, locust bean gum, guar gum, arabic gum, gelatin, pectin, starch, carboxymethyl cellulose, hydroxymethyl cellulose, It consists of one or more of hydroxypropyl cellulose, polyvinyl alcohol, polyalkylamide, polyacrylic acid and the like. Of these gelling agents, a mixture of agar, carrageenan, locust bean gum or agar alone is preferred. As the agar, elastic agar Yamato, UM-11KS, S8 (all manufactured by Ina Food Industry Co., Ltd.) and the like are used. In addition, the red algae that are the raw materials for agar may be any one or more of Amakusa, Gracilaria, Obakusa, and Itani grass. Furthermore, Amakusa is produced in Japan, Morocco, Chile, South Korea, Spain, and Ogonori is produced in Japan, Chile, South Africa, Argentina, and Ogonori is produced in Chile, Taiwan, Vietnam, China, etc., but any of them may be used. .. Furthermore, by adding lactate (sodium salt, potassium salt, calcium salt, magnesium salt), the shape retention of the gel can be further improved. Of these lactates, calcium lactate is preferred. However, in the case of agar alone, it is not necessary to add lactate.

Various functional compounds, additives and solvents can be added to the gel. Such things include, for example, insect repellents, insecticides, repellents, egg killers, synergists, stabilizers, moisturizers, preservatives, pigments, fragrances, fungicides, acaricides, deodorants, etc. Examples include air fresheners, air fresheners, and deodorants. Specifically, as room temperature volatile insect repellent essential oils, rose oil, jasmine oil, perchery oil, carnation oil, mint oil, orange oil, berga peach oil, becheba oil, spare mint oil, eucalyptus oil, cubeba oil, peppermint oil, Lemongrass oil, rosemary oil, lavender oil, lemon oil, cedar oil, pine oil, tea tree oil, cashier oil, ylang ylang oil, geranium oil, citronella oil, sardine oil, pine needle oil, terepine oil, anis oil, One or more kinds such as orange peel oil, clove oil, white platform oil, cypress oil, hinoki oil, columnus oil, henoposi oil, okotia oil, spike oil, kayapte oil, cedar wood oil and the like can be mentioned. In addition, one or more of menthol, phytoncide, limonene, pinene, anethole, carvone, cineole, turpineol, eugenol, hinokithiol, linalool, saflor, sedren, azaron and the like contained in these essential oils may be blended. .. Among these, α-pinene, spearmint oil, eucalyptus oil, cubeba oil, peppermint oil, lemongrass oil, pine oil, rosemary oil and lavender oil have an effect of expelling, invading and inhibiting spawning of adult clothing pests. Therefore, it is preferable to mix one kind or two or more kinds. As insecticides, empensulin, transfluthrin, metoflutrin, paradichlorobenzene, 2,6,6-trimethyl-2,3-epoxybicyclo [3,1,1] heptane, ε-caprolactam, imidazole, vanillin, itaconic acid, angelica Lactone, 1,7,7-trimethyltricyclo [2,2,1,0] heptane, 6,6-dimethyl-2-methylbicyclo [3,1,1] heptane, dehydroacetic acid, mandelic acid, 2-ethylidene -5 (or 6) formyl-bicyclo [2,2,1] heptane and the like can be mentioned. Examples of the repellent include DEET, fatty acid chain esters having a carbon number of 10 to 11 and a boiling point of 200 ° C. to 230 ° C., camphor, naphthalene, cyclohexane, oxime, fluorene, and acetonaphthene. Further, as an egg killing agent, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, ethylene glycol monoisobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, tri Ethylene glycol dimethyl ether, branched chain saturated hydrocarbon with 7 to 13 carbon atoms, limonene, pinen, anetol, lemon oil, bergamot oil, sardine oil, pine needle oil, peppermint oil, terepine oil, anis oil, cedarwood oil, lavender oil , Eucalyptus oil, tea tree oil, lemongrass oil, spearmint oil, geranium oil, rosemary oil, hiba oil and the like may be blended with one or more. Further, IBTA, IBTE, etc. may be blended as a synergist, BHT, BHA, etc. may be blended as a stabilizer, glycerin, etc. may be blended as a moisturizer, and salicylic acid, paraoxy, etc. may be blended as preservatives. A benzoic acid ester or the like may be blended, blue No. 1, green No. 3, yellow No. 203 or the like may be blended as the pigment, and vanillin, phenylethyl alcohol, piperonal or the like may be blended as the fragrance.

The physical properties of the gel are not particularly limited, but the mass change rate after drying of the gel is preferably 20% or more, and more preferably 30% or more. If the mass change rate is less than 20%, the solvent content is low, and the hardness of the gel is too high, so that the effect of improving the shape retention by the three-dimensional structure may not be obtained.

The composite of the present invention preferably has a vibration damping property of 80% or more, more preferably 85% or more. If the vibration damping rate is less than 80%, the vibration absorption performance becomes small, which is not preferable.

The present invention will be described in detail below with examples.
The evaluation in the examples was performed by the following method.

<Characteristics of 3D structure>

(1) Apparent volume fraction (%) of the three-dimensional structure with respect to the complex
Fill the container with water until just before it overflows, submerge the complex completely, and divide the amount of overflowed water by the specific gravity of water to determine the volume of the complex.
Next, the three-dimensional structure is taken out from the complex and the mass is measured (three-dimensional structure mass). A 1 cm square rectangular parallelepiped sample is cut out from the taken out 3D structure, and the mass is measured (3D structure mass per 1 cm ³ ). From these, the apparent volume of the three-dimensional structure is obtained using Equation 1.
Apparent volume of 3D structure (cm ³ )
= (3D structure mass) / (3D structure mass per 1 cm ³ ) ... (Equation 1)

Subsequently, the apparent volume fraction of the three-dimensional structure with respect to the complex is obtained from the volume of the complex and the apparent volume of the three-dimensional structure using Equation 2.
Apparent volume fraction (%) of the 3D structure relative to the complex
= Apparent volume of 3D structure / Volume of complex x 100 ... (Equation 2)

(2) 5% compression hardness (N / φ100 mm)
The three-dimensional structure is taken out from the complex, and a 5 cm square rectangular parallelepiped sample is cut out from the three-dimensional structure. It is shown by the stress at the time of 2.5 mm compression of the stress-strain curve obtained by compressing to a thickness of 10 mm at a compression rate of 100 mm / min with a φ100 mm compression plate using Tensilon manufactured by Orientec (n = 3). Average value).

<Gel characteristics>
(1) Mass change rate (%)
The mass of the complex after being placed in an oven at 30 ° C. for 72 hours was measured, and how much the mass changed from the mass before drying was measured.
Mass change rate (%) = (1- (30 ° C x 72 hours mass after drying / mass before drying)) x 100

<Complex characteristics>
(1) Vibration damping (%)
A 50 x 70 x 100 mm composite was placed on the table without being fixed, hit horizontally, and the displacement was measured with an OMRON sensor head (Z4M-S100) and an amplifier (Z4M-W100C). The vibration damping property was obtained from the equation. The striking strength was such that the amplitude did not exceed 0.3 mm.
Vibration damping (%) = (1- (6th amplitude / 1st amplitude)) × 100

(2) Shape retention (%)
The complex was allowed to stand at 20 ° C. for 72 hours, the height was measured, and the rate of change with respect to the original height was determined. The higher the rate of change, the lower the shape retention.
Shape retention (%) = (1- (20 ° C x 72 hours height / original height)) x 100

<Example 1>
To 150 g of pure water, 7.5 g of polyvinyl alcohol (PVA) ("DF-20" manufactured by Japan Vam & Poval) and 0.37 g of dihiroradide adipic acid (ADH) (manufactured by Mitsubishi Chemical Co., Ltd.) were added. An aqueous solution was prepared by stirring at 80 ° C. for 1 hour.
Further, the shape of the orifice on the effective surface of the nozzle having a length of 96 mm in the width direction and a length of 31.1 mm in the thickness direction is such that a solid-formed orifice having an outer diameter of 1.0 mm has a hole pitch in the width direction of 6 mm and a thickness direction. Using a zigzag nozzle with a hole pitch of 5.2 mm, Perprene GP300 (manufactured by Toyo Spinning Co., Ltd., Shore A hardness = 96) is placed below the nozzle at a spinning temperature of 200 ° C. and a single hole discharge rate of 1.5 g / min. It is discharged, cooling water is arranged 21 cm below the nozzle surface, and a pair of take-up conveyors are arranged in parallel with a stainless steel endless net having a width of 25 mm at intervals of an opening width of 25 mm so as to partially protrude above the water surface. A three-dimensional network structure is formed by winding the discharge line of the above and forming a loop to fuse the contact portions, and both sides of the molten network structure are sandwiched by a take-up conveyor every minute. After being drawn into cooling water at a speed of 5 m and solidified to flatten both sides, it was cut to a predetermined size to obtain a network structure.
A reticulated structure having a diameter of 80 mm and a thickness of 25 mm and an aqueous solution are placed in a container made of polyethylene terephthalate (hereinafter referred to as PET) having a diameter of 80 mm and a depth of 30 mm, and allowed to stand at 20 ° C. for 24 hours to gel and form a composite. Made.
Table 1 summarizes the measured characteristics.
The obtained sample was able to maintain its shape and had sufficient shape retention. In addition, it has high vibration damping properties and also has a function as a vibration damping material.

<Comparative example 1>
A sample was prepared in the same manner as in Example 1 except that the sample was prepared without inserting the network structure.
Table 1 summarizes the measured characteristics.
The shape of the obtained sample could not be maintained, and the shape retention was low.

<Comparative example 2>
To 150 g of pure water, 15 g of polyvinyl alcohol (PVA) ("DF-20" manufactured by Japan Vam & Poval) and 0.75 g of dihiroradide adipic acid (ADH) (manufactured by Mitsubishi Chemical Co., Ltd.) were added at 80 ° C. An aqueous solution was prepared by stirring in 1 hour, and a sample was prepared in the same manner as in Example 1 except that a sample was prepared without adding a network structure.
Table 1 summarizes the measured characteristics.
The obtained sample was able to maintain its shape, but could not obtain sufficient vibration damping.

The present invention relates to the shape retention of a gel, and the obtained composite can be used as a vibration absorber, an actuator, or the like by taking advantage of its characteristics, and makes a great contribution to the industrial world.

Claims (5)

A complex containing a three-dimensional structure in the gel. The complex according to claim 1, wherein the apparent volume fraction of the three-dimensional structure to the complex is 70% or more in the complex. The composite according to claim 1 or 2, wherein the 5% compressive hardness of the three-dimensional structure is 0.5 N / φ100 mm or more and 10 N / φ100 mm or less. The complex according to any one of claims 1 to 3, wherein the rate of change in mass of the gel after drying is 20% or more. The complex according to any one of claims 1 to 4, wherein the vibration damping property is 80% or more.